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Патент USA US3025153

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3,025,147
Patented Mar. 13, 1962
1
2
3,025,147
cent ASTM distillation point not greater than about 220°
F, as such gasolines normally involve a severe engine
NONSTALLING GASGLINE CQMPUSHTIQN
Gardner E. Gaston, Tarentum, and Donald W. Howard,
stalling problem.
The amine salts and polyoxyalkylene derivatives of
stabilized rosin amines whose use is included by this in
vention are polar, surface active materials‘. While the
invention is not limited to any theory of operation, it
Monroeville, Pa., assignors to Gulf Research & Devel
opment Company, Pittsburgh, Pa., a corporation of
Delaware
No Drawing. Filed Aug. 1, 1953, Ser. No. 752,442
'
it Q
8 Claims.
might appear that the addition agents disclosed herein, by
(Cl. 44-62)
virtue of their polarity, tend to orient themselves upon the
metal surfaces of the throttle valve and other critical car
This invention relates to gasoline fuel compositions, and
more particularly to gasoline fuel compositions that have 10 buretor parts contacted by the gasoline compositions, thus
reduced engine stalling tendencies at cool, humid atmos
forming a moisture-displacing residual coating upon said
pheric conditions.
carburetor parts which tend to prevent the adherence to
When an internal combustion engine is operated at cool,
said metal surfaces of accumulations of ice of such magni
humid atmospheric conditions, using a gasoline fuel hav
tude as to block the narrow air passages that exist in
ing a relatively low 50 percent ASTM distillation point,
carburetor throats at engine idling conditions. It is also
i.e., below about 235° F., excessive engine stalling is apt
considered possible that the addition agents disclosed here
to be encountered at idling speeds during the warm-up
in may tend to orient themselves about small, ice particles,
period, especially where engine idling occurs following a
thus tending to prevent the formation of macrocrystals of
period of light load operation.
Engine stalling under
ice of a size sufficient to block carburetor air passages at
such conditions has been attributed to the partial or com 20 engine idiing conditions. Although the effectiveness of
tete blocking of the narrow air passage that exists be
the herein disclosed addition agents is believed to be at
tween the carburetor throat and the carburetor throttle
tributable in some way to the particular polar, surface
valve during engine idling, by ice particles and/or solid
active characteristics thereof, this general explanation is
hydrocarbon hydrates that deposit upon and adhere to
somewhat
negatived by the fact that many other surface
the metal surfaces of the carburetor parts. Such icing of 25 active agents, including, for example, other salts and oxy
carburetor parts occurs as a result of the condensation of
moisture from the air drawn into the carburetor and as
a result of the solidi?cation of such condensed moisture.
The aforesaid condensation and solidi?cation of moisture
are caused by the refrigerating effect of rapidly evapo
rating gasoline. Accordingly, excessive engine stalling due
to carburetor icing occurs as a practical matter only in the
aikylene derivatives of stabilized rosin amines, as well as
salts of other amines than rosin amines, have little or no
effect upon the carburetor icing tendencies of gasolines.
30
The antistalling addition agents disclosed herein are
useful when incorporated in gasoline compositions of the
type disclosed in any amount su?icient to reduce the
engine stalling characteristics thereof. For example, an
instance of gasolines containing a large proportion of
improvement in the stalling characteristics of gasolines
relatively highly volatile components. in practice, the
of'the
type dis-closed herein will normally be obtained by
problem of engine stalling due to carburetor icing has 35 addition thereto of the herein disclosed addition agents
been found to be serious, under cool, humid atmospheric
in amounts of at least 0.001 percent by weight of the
conditions, in connection with gasolines having a 50 per
composition (approximately 2.5 to 2.6 lbs/1000 bbls. of
cent ASTM distillation point below about 220° F.
gasoline). Preferably the antistalling addition agents
Excessive engine stalling is, of course, a source of an
disclosed herein will be employed in proportions of at
40
noyance owing to the resulting increased fuel consump
least 0.006 percent by weight of the composition (ap
tion, battery wear and inconvenience of frequent restart—
proximately 15 lbs./1000 bbls. of gasoline). Thus, a
ing. It is therefore important that the inherent engine
stalling characteristics of gasoline fuel be reduced sub
stantially, where the 50 percent ASTM distillation point
marked improvement in the stalling characteristics of
gasolines has been obtained by incorporation therein of
tions that comprise hydrocarbon mixtures boiling in the
pounds per thousand barrels of gasoline.
addition agents of the kind disclosed herein in propor
of such gasoline fuels is sufficiently low to cause a prob 45 tions of about 15 to 25 pounds per thousand barrels of
lem in this respect.
gasoline. Normally, we prefer to employ the addition
The present invention relates to gasoline fuel composi
agents disclosed herein in proportions of about 15 to 50
Although in
gasoline range and that normally tend to promote engine
some instances, it may be desired to employ the antistall
stalling by carburetor icing, which fuel compositions ex 50 ing addition agents disclosed herein in amounts in excess
hibit reduced engine stalling tendencies, and which are
of 250 pounds per thousand barrels of gasoline, that is
thereby rendered more suitable for use as fuels in spark
0.1 percent by weight or higher, such proportions are not
ignition, reciprocating internal combustion engines. We
necessary and normally produce'no signi?cant additional
have found that such improved gasoline compositions can
improvement in the stalling characteristics of the gasoline.
be obtained by incorporating therein a small amount of 55 111 no instance sohuld the antistalling addition agents dis
an addition salt of a stabilized rosin amine and an oil
soluble hydrocarbon sulfonic acid, or by incorporating
therein a small amount of a polyoxyalkylene derivative of
a stabilized rosin amine containing per molecule about 4
closed herein be added to gasoline in amounts such as
to produce an undue adverse effect on the volatility, com
bustibility, antiknock or gum-forming characteristics of
the gasoline.
to 20, preferably 5 to 15, oxyalkylene groups that con 60
It will be appreciated that the optimum proportion of
tain 2 to 3 carbon atoms each. Salts of dehydroabietyl
the antistalling addition agents disclosed herein can vary
amine and oil-soluble petroleum sulfonic acids are ex
within the range indicated above in accordance with the
amples of preferred salts whose use is included by this
particular gasoline employed, inasmuch as the problem
invention. The polyoxyethylene derivative of dehydro
of engine stalling due to carburetor icing is a function of
abietylamine that contains about 11 oxyethylene groups 65 the 50 percent ASTM distillation point of the gasoline.
per molecule is an example of another especially effective
Thus, greater concentrations of the antistalling addition
material for the purposes of this invention. The above
agents are normally desirable with decreasing 50 percent
indicated addition agents are normally employed in pro
ASTM distillation points. The optimum concentration of
portions between about 0.001 and 0.01 percent by weight,
the lantistalling addition agents disclosed herein may also
but other proportions canbe used. The invention is im 70 vary somewhat in accordance with the particular make
portant in connection with gasolines having a 50 per
and model of engine in which the gasoline is used, as
3,025,147
3
-
4
Inspections:
well as in accordance with the severity of the atmos
pheric conditions encountered. With regard to this last
Vapor pressure, Reid, lb ________________ __
8.5
ASTM, distillation, gasoline
mentioned factor, the problem of engine stalling due to
carburetor icing resulting from the refrigerating e?ect of
evaporating gasoline upon moisture condensed from the
atmosphere has been found to ‘be serious at low tempera
Over pt. ° F _______________________ __
End pt. ° F ________________________ __
100
357
10% evaporated at ° F ______________ __
136
50% evaporated at ° F ______________ __ 200
tures, e.g., 35°, 40°, 45°, 50°, and when the relative hu
90% evaporated at ° F ______________ __ 277
midity is in excess of about 55 percent, e.g., 75 percent,
Recovery, percent __________________ __ 98.3
99 percent. The optimum proportion of the antistalling
Residue, percent ____________________ __ 1.4
addition ‘agents disclosed herein in any given case will be 10
sufficient to effect substantial reduction in the stalling
(b) The addition agent of Example 1(a) was incorpo
tendencies of the -fuel at the particular atmospheric con
rated in the base gasoline of Example 1(a) in propor
ditions of temperature and humidity which are likely to
tion of 15 pounds per thousand barrels of gasoline.
be encountered in service.
Practically speaking, the problem of engine stalling due
EXAMPLE II
to carburetor icing caused by rapid evaporation of gaso
(a)
The
addition
agent of Example 1(a) was incor
line occurs only in connection with gasolines having a
porated in a base gasoline in the proportion of 250
50 percent ASTM distillation point less than 235° F.
pounds per thousand barrels of gasoline. In this compo
While occasional engine stalling may occur as a result
of carburetor icing at severe atmospheric conditions of 20 sition the base gasoline had the following inspections.
temperature and humidity with gasolines having somewhat
Inspections:
higher 50 percent ASTM distillation points, experience
Gravity,
has indicated that the problem does not assume major
Existent gum, mg./100 ml _______________ __
Oxidation stability, minutes ______________ __
importance except with gasolines of the character in
dicated. As indicated, the problem of engine stalling due 25
to carburetor icing is especially severe in connection with
gasolines having a 50 percent ASTM distillation point of
less than about 220° F. The invention is particularly
useful in connection with such gasolines. The term “gas
° API _________________________ __ 62.6
557
Knock rating
Motor Method, octane number _______ __ 84.4
Research Method, octane number _____ __ 95.4
TEL, ml./Gal __________________________ __ 3.19
Vapor pressure, Reid, lb ________________ __
oline” is used herein in its conventional sense to include 30
8.4
ASTM distillation, gasoline—
hydrocarbon mixtures having a 90 percent ASTM distilla
Over point, “P ____________________ __
100
tion point of not more than about 392° F. and a 10 per
End
10%
50%
90%
394
135
210
316
cent ASTM distillation point of not greater than 149° F.
The antistalling addition agents whose use is included
by this invention can ‘be incorporated in the base gasoline
fuel compositions in any suitable manner.
Thus, they
point, ° F _____________________ __
evaporated at ° F ______________ __
evaporated at ° F ______________ __
evaporated at ‘’ F ______________ __
Recovery, percent ___________________ _.. 97.6
can be ‘added as such to gasoline or in the form of dis
Residue, percent ____________________ __
0.9
persions or solutions in solvents such as butanol, iso
propanol, ethanol, methanol, benzene, toluene, heptane,
kerosene, gasoline, mineral lubricating oil, or the like,
40
which solvents may or may not themselves contribute to
the antistalling characteristics of the gasoline motor fuel
composition. If desired, the herein disclosed antistalling
addition agents can be incorporated in gasoline fuel com
positions in admixture with other materials designed to
improve one or more properties of the gasoline, such as
EXAMPLE III
(a) A polyoxyethylene derivative of the stabilized ros
in amine of Example 1(a) containing about 5 oxyethyl
ene groups per molecule was blended with the base gaso
line of Example Na) in the proportion of 25 pounds
per thousand barrels of gasoline. The addition agent of
' this example contained approximately 15 percent free ros
in amine which had no signi?cant effect on the stalling
antioxidants, antigurnming agents, e.g., 2,6~ditertiarybutyl,
characteristics of the gasoline.
4-methylphenol, antiknock agents, e.g., tetraethyl lead,
(b) The addition agent of Example III(a) was incor
lead scavenging agents, e.g., ethylene dibromide, ethylene
porated in the base gasoline of Example 11 in the propor‘
dichloride, corrosion inhibitors, e.g., oil-soluble amine 50 tion of 250 pounds per thousand barrels of gasoline.
phosphates, dyes, and the like.
EXAMPLE IV
The gasoline fuel compositions of this invention can be
further illustrated by reference to the following speci?c
(a) The salt of the stabilized rosin amine of Exam
examples:
ple 1(a) and oil-soluble petroleum sulfonic acids having
EXAMPLE I
55 an average molecular weight of 392 was incorporated in
a base gasoline containing 88 percent L-4 test fuel and
(a) To a base gasoline, there was added a polyoxy
12 percent light thermally cracked gasoline distillate in
ethylene derivative of a stabilized rosin amine (Rosin
the proportion of 25 pounds per thousand barrels of
Amine D) containing eleven oxyethylene groups per mol
gasoline. The stabilized rosin amine sulfonate of this
ecule, in the proportion of 25 pounds per thousand barrels
of gasoline. The stabilized rosin amine referred to in 00 example had the following analysis:
this example was a dehydroabietylamine having the
formula:
Rosin amine sulfonate _____________________ __
52.0
Mineral oil
47.5
___-
_____
___
Inorganic salts ____________________________ __ Trace
Water
65
___-
Ash
____ __
Molecular
_
_
0.5
___
0
weight _________________________ __
709
The base gasoline of this example had the following in
\
spections.
Inspections:
Cr
Gravity,
° API _________________________ __ 65.2
Existent gum, mg./100 ml ______________ __ 2.4
Oxidation stability, minutes ______________ __ 220
The base gasoline of this example had the following
inspections.
~
TEL,
75
mL/gal __________________________ __ 2.52
Vapor pressure, Reid, lbs ________________ __
7.7
3,025,147
5
Inspections-Continued
ASTM distillation, gasoline
Table B
Over point, °F __________________ _v___ 1.01
End point, ° F____,_____
Engine test;
Fuel composition
avg. number
stalls per 20
10% evaporated at '’ F___
' cycles
50% evaporated at °F-,.____, _________ 90% evaporated at °F _____________ ._ 283
Recovery,
Residue, percent _______ _.__ ___________ __
Inspections:
°API _________________________ -_ 63.3
Existent gum, mg./ 100 ml _______________ __
Oxidation stability, minutes ______________ __
Example I(b). _ __..
_.-_
Example III(e). _-_
_.._
10 Base fuel
Example IV(a) _ . _ __..--
3. 7
4. 7
6. 7
11.8
.... _.
5. 5
From the results set forth in Tables A and B, it will
be seen that addition agents of the class described herein
15 effect a marked reduction in the carburetor icing and/or
engine stalling tendencies of gasoline compositions in
which they have been incorporated. While the addition
agents employed in the above-indicated speci?c embodi
1.6
560
Knock rating, octane number_.
ments are especially effective for the purposes of this
invention, it is to be understood that the invention is
Motor Method _____________________ __ 84.4
Research Method ___________________ __ 95.6
not limited to the use of these materials. Other addition
agents of the class described herein can be substituted
TEL, rnl./gal __________________________ __ 3.03
Vapor pressure, Reid, lbs ________________ __
10. ,2
Example 1(a) ____________________________________ _.._
1.0
(b) The addition agent of Example IV(a) was incor
porated in a base gasoline in the proportion of 250
pounds per thousand barrels of gasoline. The base fuel
of this example had the following inspections.
Gravity,
Base fuel
percent __________________ __ 97.9
7.7
for those indicated in the preceding examples in the same
or equivalent proportions with good results. For ex
ample, there can be substituted in the above-indicated
End point, ° F _____________________ __ 392
gasoline motor fuel compositions polyoxyethylene and
10% evaporated at 0F _____________ __ 139
polyoxypropylene derivatives of stabilized rosin amine
50% evaporated at “F _____________ __ 211
that contain, respectively, 20 and 7 oxyalkylene groups
90% evaporated at ° F ______________ _.. 3116
per molecule.
Recovery, percent __________________ __ 97.7 30
The oil-soluble petroleum sulfonic acids whose sta~
Residue, percent ____________________ __
1.1
bilized rosin amine salts are employed in the gasoline
motor fuel compositions of this invention are preferably
(c) The addition of agent of Example IV(b) was in
the sulfonic acids known as the mahogany acids. These
corporated in the base gasoline of Example II in the
acids, together with the water-soluble green acids, are
proportion of 250 pounds per thousand barrels of gaso
produced during the sulfuric acid re?ning of petroleum
line.
lubricating oil distillates. Methods of recovering these
The utility of the gasoline motor fuel compositions of
acids, as well as methods of making amine salts thereof,
this invention has been demonstrated by two different
are well known and form no part of the present inven
test procedures. In the one test, referred to hereinafter
tion.
as the Mock Fuel System Test, test fuel at about 50° F. 40
The term “stabilized rosin amine” as used herein is
and air at about 60° F. and 75 percent relative humidity
employed in its normal sense to mean a rosin amine
are supplied at controlled rates to a glass vaporizer cham
having the ring structure of a stabilized rosin acid, such
ASTM distillation gasoline-
Over point, "P ____________________ __
103 25
ber maintained at an absolute pressure of 12 inches of
Hg and having an initial temperature of 45° F.
as dehydroabietic acid, dihydroabietic acid, tetrahydro
The
abietic acid, or a mixture of such rosin amines, unless
time for icing to occur and/ or the amount of ice formed 45 speci?cally indicated to the contrary.
on a movable brass throttle plate in the glass vaporizer
To the gasoline fuel compositions of the present in
chamber are observed and recorded.
According to the other test procedure employed, here
inafter referred to as the Engine Test, a 216 cubic inch
vention there can be added one or more additional agents
designed to improve one or more characteristics of the
Chevrolet engine employing a standard, Carter downdraft
gasoline fuel. For example, antioxidants, antiknock
agents, ignition control additives, other de-icing agents,
carburetor is operated at no load on a test stand under
antirust agents, dyes, lead scavenging agents and the like
cycling conditions in a cold room maintained at 40° F.
can be added to the gasoline compositions of this inven
for a warm-up period of 20 cycles. Each cycle com
tion, and the invention speci?cally includes gasoline
prises 40 seconds at 2000 r.p.m. followed by an idle for
compositions
containing such additives.
20 seconds at 450 rpm. Air is supplied to the carburet 55
Numerous additional embodiments of the invention will
or at 40° F. and 80 to 90 percent relative humidity.
readily suggest themselves to those skilled in the art.
The number of engine stalls is observed and reported as
Accordingly, only such limitations should be imposed on
stalls per 20 cycles. The results obtained in the testing
the invention as are indicated in the claims appended
of the motor fuel compositions of the above-indicated ex
hereto.
60
amples are presented in the following tables:
We claim:
1. A gasoline motor fuel composition comprising a
major amount of a hydrocarbon mixture boiling in the
gasoline range and that normally tends to promote stalling
of internal combustion engines, and a small amount, suffi
65
cient to reduce the engine stalling characteristics of the
Table A
Mock fuel system test
composition of a member selected from the group con
Fuel composition
Extent of ice forma- Time to
tion on throttle plate icing, min
utcs
Base fuel ____________________________ __
Example II ____ _.
Example III(b)._
Example IV(c)_
Base
in
_ _ _ . _ . . _ . _ _
Example IV(b)..
Very heavy ..... ..
L‘ ht
sisting of addition salts of stabilized rosin amine and
an oil-soluble hydrocarbon sulfonic acid, and polyoxy
alkylene derivatives of stabilized rosin amine containing
70 about 4 to 20 oxyyalkylene groups per molecule, where
said oxyalkylene groups contain two to three carbon
7
atoms each.
15.2
1. 5
18.3
_ _ _ . _ _ _ _ . . __
__________ _.
2. The fuel composition of claim 1 Where the hydro
carbon mixture has a 50 percent ASTM distillation point
75 not greater than 220° F.
3,025,147
7
3. The fuel composition of claim 1 wherein said small
amount is 0.001 to 0.1 percent by weight of the com
position.
4. The fuel composition of claim 1 where said small
acount is about 15 to 50 pounds of said member per
thousand barrels of said hydrocarbon mixture.
5. The fuel composition of claim 1 where said member
is a salt of oil-soluble petroleum sulfonic acids and sta
bilized rosin amine.
6. The fuel composition of claim 1 ‘where said member 10
is a polyoxyethylene derivative of stabilized rosin amine
containing about 11 oxyethylene groups per molecule.
7. The fuel composition of claim 1 where said member
is a polyoxyethylene derivative of stabilized rosin amine
containing about 5 oxyethylene groups per molecule.
15
8. The fuel composition of claim 1 where said member
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,484,010
2,684,292
2,706,677
2,843,464
2,857,253
2,862,800
2,872,303
2,883,276
Bried _______________ __ Oct. 11,
Caron et al. _________ __ July 20,
Duncan et al. ________ __ Apr. 19,
Gaston et al. __________ __ July 15,
Hinkamp et al. ______ __ Oct. 21,
Cantrell et al. ________ __ Dec. 2,
Donlan ______________ __ Feb. 3,
Larsen ______________ __ Apr. 21,
1949
1954
1955
1958
1958
1958
1959
1959
FOREIGN PATENTS
791,394
Great Britain ________ __ Mar. 5, 1958
OTHER REFERENCES
Petroleum Re?ning with Chemicals, by Kalichevsky et
is a polyoxyalkylene derivative of stabilized rosin amine
al., 1956, Elsevier Pub. Co., page 480.
containing about 4 to 20 oxyalkylene groups per mole
“New Sonneborn Sulfonates” (Brochure), L. Sonne
cule, and where said oxyalkylene groups contain 2 to 3
born Sons, Inc., WO 1876-8-55, received in Pat. Off.
carbon atoms each.
20 April 11, 1956, 4 pp.
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